Polyesters are utilized in a number of applications due to their properties and their ease of synthesis. Exemplary uses include coatings, films, fibers, and resins. Due to their properties polyesters are also utilized in blends with other polymers to improve certain property limitations of the other polymers, such polymers include polycarbonates, polyamides, styrenic polymers, and polyolefins, and the like. Polyesters are typically prepared by reacting diacids with dialcohols, and generally are linear in structure. It is somewhat challenging to cross-link these polyesters due to the structure. Some crosslinking processes require special catalysts or high temperatures.
1,1-diester-1-alkenes, such as methylene malonates, contain two diester groups, and an alkylene group disposed between the two diester groups. Recent developments in synthesis of these compounds facilitate the synthesis of these compounds and their use in a variety of applications, see Malofsky U.S. Pat. No. 8,609,885; U.S. Pat. No. 8,884,051; and U.S. Pat. No. 9,108,914; incorporated herein by reference in their entireties for all purposes. Processes for transesterifying these compounds have also been recently developed. Malofsky et al. WO 2013/059473 and US 2014/0329980, incorporated herein by reference in their entirety for all purposes, discloses the preparation of multifunctional methylene malonates by multiple synthetic schemes. One disclosed process involves reacting a methylene malonate with a polyol in the presence of a catalyst to prepare compounds wherein at least one of the ester groups on the methylene malonates undergoes transesterification to react with the polyol and form multifunctional compounds (multifunctional meaning the presence of more than one methylene malonate core unit). The use of enzyme catalysis is disclosed. Sullivan, U.S. Pat. No. 9,416,091 discloses transesterification of 1,1-disubstituted-1-alkenes using certain acid catalysts, incorporated herein by reference in its entirety for all purposes.
Commonly owned application titled POLYESTER MACROMERS CONTAINING 1,1-DICARBONYL-SUBSTITUTED 1 ALKENES having a Ser. No. 15/234,191 filed Aug. 11, 2016 discloses compositions containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes useful in preparing polyesters containing compositions which can be crosslinked elegantly without the need for problematic catalysts and use relatively mild conditions. Disclosed are coatings prepared from such compositions that exhibit enhanced properties, wherein such enhanced properties include flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, ultraviolet radiation resistance, acid and base resistance, and the like. Processes that prepare the components for such coatings and the coatings are also disclosed. The compositions and processes disclosed provide significant improvements in coating technology. In order to meet customer expectations additional enhancement to this technology is desirable.
What is needed are polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes compositions useful in preparing coating compositions which can be cross-linked elegantly without the need for problematic catalysts and use relatively mild conditions. What is also needed are coatings prepared from such compositions that exhibit enhanced properties, such as flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, ultraviolet radiation resistance, high temperature acid and base resistance, fuel resistance. Processes that prepare the coatings are needed.